Dyeing hair with aqueous solution of nitro p-phenylenediamines and composition therefor

ABSTRACT

IN WHICH N IS A WHOLE NUMBER BETWEEN 2 AND 6 INCLUSIVE, AND R2 and R3, which may be identical or different, are selected from the group consisting of hydrogen, lower alkyl, lower hydroxyalkyl, and with the nitrogen atom adjacent R2 and R3 may form morpholino and piperidino, ach R1, R2, R3 having 1-6 carbon atoms on their alkyl portion, AND THE PROCESS OF DYEING KERATIN FIBERS.   IN WHICH R&#39;&#39; is selected from the group consisting of methyl and NO2, and R&#39;&#39;&#39;&#39; is selected from the group consisting of hydrogen and lower alkyl, having 1-6 carbon atoms, AND R1 is selected from the group consisting of lower alkyl, lower hydroxyalkyl, lower alkoxyalkyl, and   IN WHICH R is selected from the group consisting of lower alkyl, hydroxy alkyl, carboxyalkyl, carbethoxyalkyl, carbamylalkyl, haloalkyl, aminoalkyl, aminodialkyl, alkylaminodialkyl, alkyl morpholino, alkyl piperidino, having 1-6 carbon atoms on each mentioned alkyl portion, Z is selected from the group consisting of   A keratin fiber dye composition which comprises a solvent and a dyeing amount of a dye compound having the formula :

United States Patent [1 1 Kalopissis et a1.

[11] 3,804,586 1 Apr. 16, 1974 DYEING HAIR WITH AQUEOUS SOLUTION OF NITRO P-PHENYLENEDIAMINES AND COMPOSITION THEREFOR [75] Inventors: Gregoire Kalopissis, Paris; Andree Bugaut, Boulogne-sur-Seine; Vahan Zorayan, Enghein-les-Bains, all of France [73] Assignee: LOreal, Paris, France [22] Filed: Sept. 8, 1971 [21] Appl. No.: 178,776

Related US. Application Data [62] Division of Ser. No. 728,750, May 13, 1968, Pat. No.

[30] Foreign Application PriorityData May 16, 1967 Luxembourg 53676 May 16, 1967 Luxembourg 53677 May 16, 1967 Luxembourg 53678 52 us. Cl 8/10, 8/101, 8/102,

[51] Int. Cl. D06p 3/08, A61k 7/12 [58] Field of Search 8/10, 10.1, 10.2, 11; 260/247.1, 247.5, 294, 553

[56] References Cited UNITED STATES PATENTS 3,629,330 12/1971 Brody et a1. 260/553 A 3,632,582 1/1972 Bil 8/10 Primary Examiner-George F. Lesmes Assistant Examiner-Patricia C. Ives Attorney, Agent, or Firm-Cushman, Darby & Cushman [57] ABSTRACT A keratin fiber dye composition which comprises a solvent and a dyeing amount of a dye compound having the formula 1 NHRi in which R is selected from the group consisting of lower alkyl, hydroxy alkyl, carboxyalkyl, carbethoxyalkyl, carbamylalkyl, haloalkyl, aminoalkyl, aminodialkyl, alkylaminodialkyl, alkyl morpholino, alkyl piperidino, having l-6 carbon atoms on each mentioned alkyl portion, Z is selected from the group consisting in which R is selected from the group consisting of methyl and N0 and R" is selected from the group consisting of hydrogen and lower alkyl, having 1-6 carbon atoms,

and R is selected from the group consisting of lower alkyl, lower hydroxyalkyl, lower alkoxyalkyl, and

/R2 z)=-N\ 4 Claims, N0 Drawings DYEING HAIR WITH AQUEOUS SOLUTION OF NITRO P-PHENYLENEDIAMINES AND COMPOSITION THEREFOR This a division, of application Ser. No. 728,750, filed May 13, 1968, now U.S. Pat. No. 3,617,164.

It is an object of the present invention to provide a new chemical compound responding to the formula:

in which R represents a lower alkyl, which may or may not be substituted, and in particular ahydroxyalkyl, carboxyalkyl, carbethoxyalkyl, carbamylalkyl, halogenoalkyl or aminoalkyl radical. The aminoalkyl may, or may not be substituted on the amine function, the nitrogen atom of which may form part of a heterocyclic ring. In the above formula Z may be an radical, or a radical, with R representing a hydrogen atom, a methyl group, or an NO group, and R" representing a hydrogen atom, or a lower alkyl, while R represents a lower alkyl, a lower hydroxyalkyl, a lower alkoxyalkyl, or a chain in which n is a whole number between 2 and 6 inclusive, and R and R which may be identical or different, "represents a hydrogen atom, a lower alkyl, or a lower hydroxyalkyl, while the nitrogen atom adjacent R and R may form therewith a heterocyclic radical such as a morpholino or piperidino radical, the radicals of the alkyl portions of the radicals R, R", R,, R, and R having 1-6 carbon atoms.

Another object of the present invention is to provide new quaternary derivatives corresponding to the compounds of formula (I), when these compounds have a quaternizable tertiary amine function.

It should be noted that the compounds of formula (I) are particularly adapted to be used to dye keratinic fibers in general, and especially hair. They have an excellent affinity for keratinic fibers, good stability when exposed to light and inclement weather, and are readily soluble in water.

A further object of the present invention is to provide a composition for dyeing human hair essentially characterized by the fact that it comprises, in solution, at least one dye selected from the group consisting of the compounds responding to formula. (I) and their quaternary derivatives.

The dyeing compositions according to the invention are preferably simple aqueous solutions having a pH value lying generally between 4 and 10, and preferably between 7 and l0.

Moreover, the dyeing compositions according to the invention may comprise various ingredients currently used in hair dyeing compositions, such for example as organic solvents, thickening agents, detergents, emol lients, perfumes and lacquers. The dyes according to the invention may also be mixed with each other and with other dyes such as nitro dyes, azo dyes, anthraquinone dyes, or any other type of dye conventionally used to dye hair.

. The application of these dyeing compositions to the hair does not necessitate the addition of an oxidizing agent. The time of contact with the hair may vary within broad limits, but falls preferably between -S and 30 minutes. The temperature at which said compositions are applied may also be varied, but they are preferably used at room temperature. The concentration of the dye may be varied within broad limits, but lies preferably between 0.1 and 3 percent by weight.

It is a further object of the present invention to pro vide a method of dyeing hair essentially characterized by the fact that a dyeing composition as here'inbefore defined is applied to the hair for between 5 and 30 min-' utes, and the hair is then washed, rinsed, and dried.

The present invention also comprises a method of preparing the compounds of formula (I) essentially characterized by the fact that, in the first step parahalogenometanitranilines or arylsulfonamides responding to the formula:

in which R' has the significance hereinbefore indicated, and X represents a halogen atom (preferably chlorine). are alkylized. This step is followed in the case of the arylsulfonamides of formula II, by acid hydrolysis, so as to obtain a compound responding to the formula:

IFIHR in which X and R have the significance hereinbefore indicated. Then, in a second step, the compound according to formula III is amidified to transform it into a derivative responding to the formula:

- IIIRZ X (IV) in which X and R have the significance hereinbefore indicated and Z represents either an radical in which R" has the significance hereinbefore indicated. This is followed by a third step in which the compound of formula IV is reacted with an amine having the formula R,NH in which R has the significance hereinbefore indicated.

The compounds responding to formula (I) may be quaternized in a conventional manner, using a quaternizing agent such as methyl sulfate or an alkyl or aryl halide.

It is also an object of the present invention to provide the intermediates obtained in the course of the above described process, per se. In particular, it is desired to obtain chemical compounds responding to the formula:

IIIHR (III) and their salts (particularly their hydrohalides) as well as the chemical compounds responding to the formula:

IIIRZ and their salts (particularly their hydrohalides). In these formulae R, X and Z have the significances hereinbefore indicated.

The present invention also encompasses the methods of making the new intermediates responding to formulas (Ill) and (IV). These processes consist of the first and second steps of the method of making the compound of formula (I), as hereinbefore described.

In order that the invention may be better understood, several examples of methods of making the intermediates of formulas (III) and (IV)'and the final compound of formula (I), as well as several dyeing compositions made with the compounds of formula (I) will now be described.

In the first series of examples, the preparation of several compounds responding to formula (III) will be described.

EXAMPLE I Preparation of 2-nitro-4-N-B-hydroxyethylamino chlorobenzene by direct alkylation.

A mixture containing 0.070 mo] (12 g) of 2-nitro-4- amino chlorobenzene is heated in a boiling water bath with 0.14 mol (25 g) of percent glycol bromohydrin, 10 cc of water and 7 g of calcium carbonate. After heating for two hours, 0.14 mols of 70 percent glycol bromohydrin and 7 g of calcium carbonate is added and the heating continued for another two hours. After cooling, 150 cc of normal hydrochloric acid is poured in, and the mixture filtered. After alkalizing with ammonia, drying yields 13.5 g of a product which contains a little 2-nitro-4-N-B-hydroxyethylamino chlorobenzene. After recrystallization in a mixture of water and ethanol, 2-nitro-4-N-B-hydroxyethylamino chlorobenzene is obtained. This melts at 72C and is the same as the product hereinafter described in Example 4.

EXAMPLE 2 Preparation of 2-nitro-4-N(B-diethylaminoethyl)- amino chlorobenzene by direct alkylation This product is prepared by adding diethylaminoethyl hydrobromide to a solution of 2-nitro-4-amino chlorobenzene in the presence of calcium carbonate in water and alcohol which has first been brought to reflux. After keeping this at reflux for nine hours, it is boiled dry. The filtrate is cooled, and the desired product is isolated in the form of its monohydrobromide. The corresponding base prepared from this monohydrobromide is an oil, which is dissolved hot in a l/l0 normal solution of hydrochloric acid. After cooling, drying yields the monohydrochloride of 2-nitro-4-N- (B-diethylaminoethyl.)-4-amino chlorobenzene which after recrystallization in 1/10 normal hydrochloric acid, melts and decomposes at 191C, and is the same as the product hereinafter described in Example 5.

EXAMPLE 3 Preparation of N-methyl-parachlorometanitraniline par alkylation with arylsulfonamides First step: alkylation 0.4 mol g) of 2-nitro-4-benzenesulfonylamino chlorobenzene is dissolved in 600 cc of a normal sodium hydroxide solution at 30C. l.6 mols (125 cc) of methyl sulfate is added little by little, while keeping the temperature between 35 and 40C and the pH value near 9 by successive additions of a normal sodium hydroxide solution. The reaction mixture is then left to stand for 6 hours at room temperature. Cooling, drying and washing then yields 138 g of crude 2-nitro-4-N-methyl-N-benzene sulfonylamino benzene which, after recrystallization in ethyl acetate, melts at 1 19C. Analysis of this product shows the following results:

Analysis Calculated for Found Analysis Calculated for Found c,,H,,N,c1so, C,,H,N,0,C1

H 3.37 3.43 3.52 H 4.15 4.08 4.23 N 3.57 8.27 8.46 N 12.93 13.04 12.98

Second step: Hydrolysis 10 EXAMPLE 5 0.168 mol (55.2g) of 2-n1tro-4-(N-methyLN-benzyl- I sulfonyl)amino chlorobenzene is added little by little, preParatlon of B to 275 cc of sulfuric acid at 0C. When it is completely )afmm) chlorobenzene lonohydmchlonde y y dissolved, the reaction mixture is left standing for 12 ano'n of an y sulttonamlde hours at room temperature, and then poured into two 15 Flrst Step1 alkylatlonliters of ice water, after which it is alkalized with a 5 times normal solution of sodium hydroxide. Drying and washing with water yields 3 8.5 g of 2-nitro-4-N-methylamino chlorobenzene, which melts at 56C. Analysis of the product yields the following results:

parachlorometanitraniline by alkylation of an arylsulfonamide First step: Alkylation 0.097 mol (30 g) of 2-nitro-4-N-benzenesulfonylamino chlorobenzene is dissolved in 195 cc of aone-half normal sodium hydroxide solution which has first been brought to 60C. While maintaining the reaction'mixture at this temperature, 0.5 mol (333 cc) of glycol chlorohydrin is added drop by drop while stirring vigorously. A five times normal sodium hydroxide solution is added simultaneously to keep the pH between 10.5 andll. The mixture is maintained at 60C for about 5 hours and then left standing for 12 hours at room temperature. Drying and washing with water yields 34 .g of 2-nitro-4-(N-B-hydroxyethyl-N- benzenesulfonyl)-amino chlorobenzene which, after recrystallization in methanol, melts at 119C. Analysis of the product yields the following results:

Analysis 1 Calculated for Found C H,,N,O,,S Cl

0.1 mol (31.25 g) of 2-nitro-4-N-benzenesulfonylamino chlorobenzene is dissolved in 100 cc of a twice normal sodium hydroxide solution which has first been brought to 60C. While maintaining the reaction mixture at this temperature 0.16 mol (27.5 g) of diethylaminoethylchloride hydrochloride in aqueous solution, is added drop by drop, together with cc of a twice normal sodium hydroxide solution which serves tokeep the pH sufficiently alkaline. This reaction mixture is kept at 60C for 30 minutes, cooked, acidified with concentrated hydrochloric acid, and, when then dried, yields 36.5 g of the desired product in the form of its hydrochloride. This crude hydrochloride is purified by crystallation in water, and then converted by addition of a twice normal solution of sodium hydroxide into 2- nitro-4-(N-B-diethylaminoethyl-N-benzenesulfonyl) amino chlorobenzene which, after vacuum drying on P 0 melts at 43C. The analysis of this product yields the following results:

Analysis Calculated for Found C H N O S Cl Analysis Calculated for Found ll lll a l l In a second series of examples the method of preparing several intermediate compouns responding to formula (IV) will now be described.

EXAMPLE 6 Preparation of (N-methyl-N-acetyl)parachlorometanitraniline 0.19 mol of N-methyl-parachlorometanitraniline, prepared as set forth in example 3, is dissolved in 70 cc of acetic anhydride. This is heated for 15 minutes in a boiling water-bath, and poured into 700 cc of water. Drying then yields 35 g of 2-nitro-4-(N-methyl-N- acetyl)amine chlorobenzene, which melts at 114C.

EXAMPLE 7 Preparation of 2-nitro-4-(N-methyl N- benzenesulfonyl)-amino chlorobenzene 0.19 mol (35.5 g) of N-methylparachlorometanitraniline prepared as set forth in example 3 is dissolved in 175 cc of pyridine. 0.5 mol (88.25 g) of benzenesulfochloride is added. After heating to reflux for 5 minutes the mixture is cooled, and drying yields 60 g of 2-nitro-4-(N-methyl-N- benzenesulfonyl)-amino chlorobenzene which, after recrystallization in ethyl acetate, melts at 1 19C.

EXAMPLE 8 EXAMPLE 9 Preparation of 2-nitro-4-(N-acetyl-N-B-acetoxyethyl)- amino chlorobenzene 0.04 mol (8.6 g) of 2-nitro-4-B-hydroxethylamino chlorobenzene is heated for an hour in a boiling water bath while in solution in cc of acetic anhydride. After driving off the excess of acetic anhydride under vacuum, the residue is dissolved by heating it in a mixture containing 40 percent hexane and 60 percent benzene. After cooling, drying yields 10.5 g of 2-nitro-4- (N-acetyl-N-B-acetoxyethyl )-amino chlorobenzene which, after recrystallization in the benzene hexane mixture, melts at 60C. Analysis of this product yields the following results:

Found Analysis Calculated for C,,H ,,N,O,,Cl

C% 47.92 48.00 48.04 N% 9.31 9.50- 9.45 H% 4.32 4.45 4.40

In a .third series of examples the preparation of certain compounds responding to formula (I) will now be described:

EXAMPLE 10 Analysis Calculated for Found C H ,N SO,Cl

The above-described monohydrochloride is treated for 2 hours with a twice normal sodium hydroxide solution, while stirring vigorously. The sodium hydroxide solution is then extracted with methylisobutyl ketone. The methylisobutyl ketone, which contains the desired product in solution in the form of its base, is washed with water, dried on sodium sulfate, filtered, and the solvent driven off under vacuum to yield-the base in the form of a red oil.

EXAMPLE 11 Preparation of methyl-B-lN-(2-nitro-4-N-methyl-N'- benzenesulfonyl-amino)phenyl]-aminoethyl methyldiethylammonium sulfate In order to carry out this synthesis, the product obtained at the end of example 10 of the present application is used. 0.148 mo] (60 g) of l-N-B- diethylaminoethylamino-2-nitro-4-(N'-methyl-N'- benzenesulfonyl)amino benzene is dissolved in 600 cc of cold chlorobenzene and 0.164 mol (16 cc) of methyl sulfate is added drop by drop, while stirring. The reaction mixture is left standing for 24 hours at room temperature. Drying and washing with a little chlorobenzene then yields 74 g of the desired ammonium salt, which melts at 137C. Analysis of this product yields the following results:

Analysis Calculated for Found CZIHIIZN4OHSZ EXAMPLE 12 Analysis Calculated for Found CISHI'INSOSS EXAMPLE 13 Preparation of l-N-'y-methoxypropylamino-2-nitro-4- (N'-methy1-N'-benzenesulfonyl)amino benzene 0.1 mol (32.65 g) of 2-nitro-4-(N-methyl-benzenesulfony1)amino chlorobenzene which has been prepared as indicated in Example 7, is introduced little by little, while stirring, into 2 mols (178 g) of y-methoxypropylamine which has first been heated to 95C. The reaction mixture is kept in a boiling water bath for minutes, cooled, and 200 cc of ice water is then poured in. The product is an orange-colored oil, which crystallizes very easily. Drying yields 37 g of practically pure l-N-'y-methoxypropylamino-2-nitro-4-( N '-methyl- I Nbenzenesulfonyl)amino benzene, which, after recrystallization in alcohol, melts at 76C. Analysis of this product yields the following results:

Found Analysis Calculated for l'l ll il fi EXAMPLE 14 Analysis Calculated for Found ii n u t C b 55.52 55.77 55.54 H l: 6,76 6.85 6.83 N% 14.95 15.11-15.0l

EXAMPLE l5 LII - Preparationof :l-N-B-diethylaminoethylammo-2-nltro- 4-( N '-B-diethylaminoethy1 N '-benzenesulfonyl )amino benzene W 0.05 mol (20.5 g) of 2-nitro-4-(N-B- diethylaminoethyl-N-benzenesulfonyl)-amino chlorobenzene, prepared as described in Example 8, is introduced into 0.5 mol (58 g) of diethylethylenediamine which has first been heated to C. The reaction mixture is kept at this temperature for 30 minutes. The excess of aliphatic amine is driven under vacuum and the oily residue is poured into 200 cc of water. This yields the desired product in the form of a thick oil. The water is decanted; the oil is dissolved in normal hydrochloric acid; the hydrochloric acid solution is filtered and alkalized with a five times normal sodium hydroxide solution. The desired product is then extracted, using methylisobutylketone and the solvent driven off under vacuum, yielding 22.6 g of practically pure lN-B- diethylamino-ethylamino-2-nitro-4-( N -B- diethylaminoethyl-N'-benzenesulfonyl)-amino benzene in the form of a very thick oil. Analysis of this product yields the following result:

Preparation of 1-N-'y-hydroxypropylamino-2-nitro-4- (N-methyl-N-acetyD-amino benzene 0.1 mol (22.9 g) of .2-nitro-4-(N-methyl-N-acetyl)- amino chlorobenzene, prepared as described in Example 6 is introduced, while stirring, into 2 ;mols g) of propanolamine, which has first been heated to 95C. When this addition has been completed, the mixture is kept .at 95C for 10 minutes, cooled, and poured into 1.5 liters of ice water. It is then acidified with hydrochloric acid, whereupon drying and washing with water yields 25 g of l-y-hydroxypr0py1amino-2-nitro-4-(N- methyl-N-acetyl)-amino benzene which, after recrystallization in toluene, melts at 122C. Anaylsis of this product yields the following results:'

Analysis Calculated for Found CIZHIINIO4 C 53.93 54.14 53.93 H -'6.37 6.37 6.54 N 15.73 15.91 15.80

EXAMPLE 17 hydroxyethyl-N'-benzenesulfonyl) amino benzene monohydrochloride which, after recrystallization in propanol containing 2 percent water, melts and decomposes at 178C. Analysis of this product yields the following results:

Analysis Calculated for Found C H N O S Cl Several examples will now be given showing how the compounds of formula (1 are used in hair dyeing compositions.

EXAMPLE 18 The following composition is prepared:

l-N-B-diethylaminoethylamino-2-nitro-4N'-hydroxyethyl- 0.37 g amino benzene dihydrochloride 1-N-y-hydroxypropylamino-2-nitro-4-(N'-methyl-N 0.26 g acetyl)am ino benzene lsooctylphenylpolyethoxyethanol 1.2 g Na Co q.s.p. pH 8 Water, q.s.pi 100 g This composition is applied to bleached hair and left thereon for 10 minutes. The hair is then rinsed and This composition is applied to 100 percent white hair for minutes. The hair is then rinsed and shampooed and a deep blonde shade results.

EXAMPLE The following dyeing composition is prepared:

l-diethylaminocthylamino-2-nitro-4-N,N- E 11.50 dihydroxyethylamino benzene dihydrochloride Methyl-fi-[N(2-nitro-4-N'-methyl-N'-benzenesulfonyl- 0.l4 g amino)-phenyl]-aminoethyl-methyldiethylammonium sulfate lsooctyl phenyl polyethoxy ethanol 1.2 g Monoethanolamine, q.s.p. pH 7.5 Water. q.s.p. 100 g This composition is applied to bleached hair and left thereon for ten minutes. The hair is then rinsed and shampooed.

A deep mahogany blond results.

EXAMPLE 21 The following dyeing composition is prepared:

l-N-fi-diethylaminoethyl 0.25 g amino-2-nitro-4-N-hydroxy-ethylamino benzene ls o oci yl phenyl polyethoiryethanol 1.2 g Lactic acid q.s.p. pH 4 Water q.s.p. g

This composition is applied to bleached hair and left thereon for 10 minutes. The hair is then rinsed and shampooed.

A purple-violet color results.

The dyes of the invention can be also applied to normal colored hair and without using an oxidizing agent.

The following dye compounds illustrate the compounds of the invention containing respectively the R, Z, R, R", R R and R radicals as before mentioned: 1-N-B-hydroxyethylamino-2-nitro-4-(N '-methyl-N benzenesulfonyl )amino benzene: l-N-B- diethylaminoethylamino-2-nitro-4-(N -B- hydroxyethyl-N'-benZene-sulfonyl)-amino benzene:

2-nitro-4-(N-acetyl-N-B-acetoxyethyl)-amino chlorobenzene: methylamino-l ,nitro-2,(N,N- methyl,carboxymethyl)amino-4,benzene: N- methylamino-l ,nitro-2,(N-benzenesulfonyl,N-B- bromoethyl)-amino-4, benzene: 2-nitro-4-N-(B-diethylaminoethyl)-amino chlorobenzene: l-N-B- diethylaminoethylamino-2-nitro-4(N-B- diethylaminoethyl-N'-benzenesulfonyl)amino benzene: l-N-'y-methoxypropylamino-2-nitro-4-(N '-methyl-N benzenesulfonyl)amino benzene: l-N-B- diethylaminoethylamino-2-nitro-4-(N '-methyl-N benzenesulfonyl) amino benzene.

The following organic solvents may be used as solvent in the dye composition of this invention: benzylic alcohol, phenethyl alcohol, 2-butoxyethanol, cyclohexanol and the like.

The ingredients which may be added to the dye composition of this invention of the conventional type and particularly of the dyes selected from the group consisting of nitro dyes such as 1-hydroxy-2-amino-5-nitro benzene, azo dyes such as Supracide (Compagnie Francaise des Matieres Colorantes), Supramine (Societe Bayer), Cibacete (Societe Ciba) and Solacete (Imperial Chemical Industries Ltd), and anthraquinone dyes such as:

Solway (Imperial Chemical Industries Ltd.),

Cellit (B.A.S.F.) and Fenacet (General Dye Corp. N.Y.), and the like.

The following compounds illustrate the intermediate compounds of the invention:

l-chloro-2-nitro-4-(N-methyl-N-acetyl)-amino benzene:

l-chloro-2-nitro-4-( N-methyl-N-benzenesulfonyl amino benzene:

l chloro-2-nitro-4-(N-diethylaminoethyl- N'benzenesulfonyl)amino benzene:

l chloro-2-nitro-4-(N-carbomethoxy-ethylN-acetyl) amino benzene:

l chloro-2-nitro-4-( N-carbethoxy-ethyl-N benzenesulfonyl)amino benzene: l chloro-2-nitro-4-( N-bromoethyl-N- benzenesulfonyl)amino benzene: and they have the respective formulas:

What is claimed is: 1. A composition for dyeing keratinic fibers which comprises an aqueous solution of a dye of the formula wherein R is selected from the group consisting Oscarboxyalkyl, carbethoxyalkyl and carbamylalkyl wherein the alkyl moiety of each has 1-6carbon atoms,

Z is selected from the group consisting of and in which n is a whole number between 2 and 6 inclusive, and R and R are selected from the group consisting of hydrogen, lower alkyl and lower hydroxyalkyl, wherein the alkyl moiety of each has 1-6 carbon atoms, said dye being present in amounts of about 0.1 3 weight percent of said composition.

2. The composition of claim 1 having a pH between 4 and 10.

3. The composition of claim 1 'having a pH between 7 and 10.

4. A process for dyeing hair comprising applying to said hair in amounts effective to dye said hair a composition having a pH of 4-10 and comprising an aqueous solution of a dye of the formula wherein R is selected from the group consisting of carboxyalkyl, carbethoxyalkyl and carbamylalkyl wherein the alkyl moiety of each has 1-6 carbon atoms,

Z is selected from the group consisting of kyl, lower hydroxyalkyl, wherein the alkyl moiety of each has l-6 carbon atoms and in which n is a whole number between 2 and 6 inclusive, and R and R are selected from the group consisting of hydrogen, lower alkyl and lower hydroxyalkyl, wherein the alkyl moiety of each has l-6 carbon atoms, said dye being present in amounts of about 0.l-3 weight percent of said composition, permitting said composition to remain in contact with said hair for a period of about 5-30 minutes and thereafter washing, rinsing and drying said hair. 

2. The composition of claim 1 having a pH between 4 and
 10. 3. The composition of claim 1 having a pH between 7 and
 10. 4. A process for dyeing hair comprising applying to said hair in amounts effective to dye said hair a composition having a pH of 4-10 and comprising an aqueous solution of a dye of the formula 